Patent GB-534970-A (GB)
Title: Process for refining hydrocarbon oils and derivatives
IPC: C10G35/06
Filed: 1939-06-22
Abstract: 534,970. Motor fuel. OCON, E. A. June 22, 1939, No. 18179. Drawings to Specification. [Class 2 (iii)] A high anti-knock motor fuel is prepared by a process which comprises cracking petroleum hydrocarbons to produce high boiling products, normally gaseous hydrocarbons and gasoline vapours including unsaturated hydrocarbons, adding to the separated gasoline vapours and gases some oxygen-containing aliphatic compounds obtained from partially oxidized unsaturated hydrocarbons boiling mainly below the gasoline range, and reacting the resulting mixture with a reducing gas composed predominantly of hydrogen and partly of carbon monoxide under dehydrating conditions in the presence of an alkaline metal base and a metal oxide dehydration catalyst. A complete plant is diagrammatically described including cracking coils, and also the oxidation of a naphtha distillate withdrawn from the initial flash chamber by means of mild oxidizing agents such as steam or air in presence of catalysts. These oxidation products are augmented by oxygen containing aliphatic compounds obtained by oxidation of natural gas, by processing of olefines with sulphuric acid to form alcohols, in the formation of alcohols from fermentation of plant carbohydrates or in the synthesis from hydrogen and carbon monoxide. The dehydration catalyst preferably employed is a difficultly reducible oxide such as an oxide of a divalent metal such as zinc oxide, and the oxides of thoria, aluminia, silica, and magnesia. Anhydrous salts may also be used such as the sulphates or phosphates of Mg, Al., Ca, Cu. Compounds mentioned include AlPO 4 , MgP  2 O 7,  Mg, 3 (PO 4 ) 2 ,Ca  3 (PO  4 ) 2  and copper uranium phosphate. The alkylation is preferably carried out at temperatures of 400‹-1000‹ F.. and at pressures from 1-100 atmospheres, for a contact time of 5-10 minutes. In an example a propane and butane cut is passed from a bubble tower stabilizer together with uncondensed carbon monoxide and hydrogen synthesis products including about 10 per cent. methanol, 5 per cent. ethanol, with some aldehydes and about 1.5 mols. of hydrogen to 1 mol. of carbon monoxide into an alkylation zone at about 600‹-800‹ F. under a pressure of 5 atmospheres for a contact time of 20-80 seconds over a catalyst composed of 10 per cent. alumina, 20 per cent. silica gel, 50 per cent. zinc oxide and 20 per cent. potassium carbonate. The reaction products are fractionally condensed and yield about 4 galls. of motor fuel distillate per 1,000 feet of initial gas. Specification 524,613, [Group III], is referred to. The Provisional Specification also describes in detail the oxidation of the naphtha distillate referred to above, and mentions for this purpose the use as catalysts divalent metal oxides including the oxides of copper, titanium, chromium, tungsten, vanadium, germanium, silica and cerium, also zaolites containing such metals. In addition a synthesis treatment is described for producing the aliphatic oxygen containing compounds used in the main alkylation process of the invention. This includes the condensation of carbon monoxide and hydrogen in the presence of catalysts such as iron or cobalt activated by a weak alkaline oxide such as zinc oxide, chromium oxide or an alkaline carbonate. Mixed catalysts mentioned for this purpose include cobalt-copper-manganese, cobalt-thorium, cobalt-thoriumcopper, and cobalt-manganese. Suitable absorbent carriers such as magnesia, pumice, and diatomaceous earth may also be used. Specification 518,263, [Group III], also is referred to.